Method for improving textile material



Patented a... 1941 METHOD FOR IMPROVING TEXTILE Winlrid Hentrlch,Dusseldori-Reisholr, Richard Hueter, Dessau-Rosslau-in-Anhalt, andHeinl- Joachim Engelbrecht, Dessau-in-Anhalt, Germany, assignors, bymesne assignments, to. Heberlcin Patent Corporation, New York, N. Y., acorporation or New York No Drawing. Application February 19, 1938, Se-

rial No. 191,494. 193'! 9 Claims.

. higher molecular alkyl groups. The impregnations obtained in this wayare fast to a slight washing with soap as well as to the action offat-solvents such as benzine or the like.

Now it has been found that analogous effects are obtainable in a veryeasy and advantageous manner by impregnating the textile material with acarbodiimide compound containing at least one higher molecular aliphaticradical having no less than 10 carbon atoms.

The substances found-valuable are carbodiimide compounds containing atleast one higher molecular aliphatic radical having no less than 10carbon atoms. The carbodiimide radical may be combined directly orthrough any suitable atoms or atomic groups with one or several highermolecular alkyl radicals.

It is of course not necessary that the alkyl radical be of a homogeneousnature. The alkyl radical will vary according to the nature of the of adiiferent chain-length. The chain length varies according to theinitial'applied material.

Compared with the substances hitherto suggested and particularly withthe esters of isocyanic acid and isothiocyanic. acid thediphenyl-carbodi-imides oiler-the advantage of being easily accessible.For instance it would be sufllcient to treat with carbon disulflde andan aniline which may be alkylated in the nucleus ("alkyP containing noless than 10 C atoms) and to separate hydrogen sulfide fromthe reactionproduct according to the well-known Unsymmetrical mono-substituteddial'Yl-varbodi imides are obtainable in the same way fromtheunsymmetrical thio-carbamides. The unsymmetrical thio-carbamides areproduced according to the well-known method by the reaction ofphenyl-mustard oil upon alkyl-substituted anianiline and obtainedaccording to the method of Germany February 19,

lines or the like. The course of reaction is quite smooth. In a similarway the phenyl-carbodiimides are developed from phenyl-isocyanic acidesters by heating to higher temperatures. 'The action of the substanceswill not be impaired if the higher molecular alkyl residue is notsubstituted directly in the nucleus as itmay be bound indirectly, to thephenyl nucleus by means of another atom or another atom grouping. As anexample from carbon disulflde and alkyl-ethers of the amide-phenols,which after the de-sulfurization with lead-carbonate result as highmolecular alkoxyl-phenyl-carbodi-imides'. .Those substances are appliedpreferably in indifferent solvents such the like. a

In the further development of this invention it has also been found thatthe effect produced by diaryl-carbodi-imide derivatives, can likewise beobtained with difiereritly substituted carbodiimides, providedtheycontain at least one alkylresidue with no less than 10 C atoms. Thusfor example, aryl-alkyl-carbodiimides. are produced with one or severalalkyl-substituents containing no less than 10 C atoms, which alkylsubstituents may bebound on the aromatic nucleus as well as i on the nototherwise substituted nitrogen atom. The higher moleculardialkyl-carbodiimides are also useful in the same above described sense.Derivatives of cyanamide may be designated by the formula HN=C=N.R,where R contains an alkyl residue of not lessthan ten carbon atoms.These substancesmay also be employed in our process as they are in factcarbodiimide derivatlves.

The preparation of said substances is performed by well known methods.that is, by de- 4 sulfurization of the corresponding thio-carbamideswith lead-oxide. lead-carbonate or mercuric oxide. The reaction followsin most cases in a practically quantitative yield. Only the merealiphatic thio-carbamides offer some difflculties in the de-sulfurizingaccording to this method, as a substitution of the sulfur atonr byoxygen often takes place,- so that carbamide-de- Y rivatives aresimultaneously developed, The

carbodiimides' are applicable either after'separating those indifierentby-products or mixed with such accompanying bodies.

Example 1 1.4 kgs. of cetyl-aniline (containing octadecy'lthere may-becited the substances obtainable as benzol, benzine, chlorinatedhydrocarbons or the treatment of textiles with high molecularmother-solution.

, til the development of hydrogen-sulfide ceases completely. While stillwarm the cetyl-phenyl-B thio-carbamide forms crystals of the lamellarshape. After sucking off the liquid and drying the crystals 6 kgs. oftoluol are brought in without previously cleaning the crystals. In orderto convert into the di-(cetyl-phenyl) carbodiimide 1.4 kgs. oflead-carbonate are brought into the toluol-solution at 100 C. whilebeing stirred. The stirring is continued at this temperature until asample filtered ofi results after evaporating as awax-like residue solidat roomtemperature and free of sulfur. Then by filtration theleaf-sulfide is separated oil. The thus obtained solution can be applieddirectly as For impregnating-purposes it is diluted with benzol, benzineor the like up, to A2 to 1%.

With a solution diluted in the aforesaid manner light fibers are treatedat room-temperature for approximatelylO minutes, and heavy fibers up tohalf an hour. Then they are squeezed out and dried at 80-100 C.,whereupon one continues heating for 1 to 2 hours at 110125 C.

Fibers of artificial silk get particularly water- Example 2 1.2 kgs. ofhexa-decyl-p-amidophenol ether, 4.5 kgs. of carbonic disulfide and 0.015kg. of sulfurpowder are heated to a slight boiling until the developmentof hydrogen-sulfide ceases completely. After cooling one sucks off theremaining liquid and the deposit is washed out with spirit. 'The thusresulting hexa-decoxy-phenylthio-carbamide (boiling point 139.5 C.) inthe form of colourless lamellar crystals is dissolved without furtherpurification in 5 kgs. of toluol, and treated with an excessoflead-carbonate (1 kg.) at about 100 C. while being stirred for 30 to 40minutes. The thus formed lead-sulfide is filtered off. The approximately18-20% solution if evaporated leaves, at room temperature, a solidwaxlike substance.- Instead of evaporating it may be diluted for usewith benzine or benzol to the desired-proportion for use.

, 0.25% of fatty acid, no diminution of those properties could beobserved. Mixed fibers consisting of wool and cotton and treated in thesame way became likewise strongly water-repellent. This impregnationalso proved fast to washing with benzine.

' Example 3 A mixture of 0.67 kg. of phenyl-mustardoil and 1.6 kgs. ofcetyl-p-amido-phenyl ether is dissolved in 6 kgs. of benzohand keptboiling under a reflux condenser for 2 hours. Then with mechanicalstirring it is treated with lead-carbonate (about 2.8 kgs.) until asample filtered off leaves hexadecoxy-allyl-thiocarbamide a residue freeof sulfur, whereupon the mixture is filtered.

The effects obtained with a dilution of the filtrate containing 1% ofsolid substance, in treating viscose-silk, cotton materials orwoolen-fibers are, after drying and subsequent treatment at atemperature up to 120 C., in exact accordance with those described inExample 2.

Example 4 To produce a dilauryl-carbodiimide suitable for the purpose ofthe present invention we avail ourselves of monolauryl-amine (technical.boiling point 0.8 mm. :96.5 to 97.5 C.). By treatment with carbondisulfide it changes over into lauryl-dithio-carbamide-acidlauryl-amine, which when heated up to 1l0-120 C. formsdi-laurylthio-carbamide (boiling point, after re-crystallization fromalcohol, 80.5"). This is now converted into dilauryl-carbodiimide byfurther treatment with an excess of ten times the weight of mercuricoxide at a temperature of -120" C. The isolation of the carbodiimide(yellowish oil slowly solidifying when kept at room temperature) isobtained by dissolving it in cold benzol from the reaction-mixture. Forthe impregnation we takea 0.5-1%-solution in benzol. The material is.agitated in this solution for 10 minutes at 20-30 C., whereupon it iscentrifuged and dried. By heating the material for 1 hour up to 110-120the fixation of the impregnation will occur. This impregnation impartsto woolen cloths, mixed fibers and artificial silk materials theproperty of water-repelling to asurprisingly high degree. Thisimpregnation proved fast to a. mild soap-washing as well as tobenzine-washing.

Example 5 A mixture of 2' kgs. of hexadecyl-p-amidophenol ether, 1 kg.of allyl-mustard -oil and 4 kgs. of toluol are heated to 100 C. for 5hours, whereupon the solvent is removed by distilling. After cooling theresidue is stirred with ether and the liquid sucked off. The thusresulting (boiling point 965) in the form of light powder is treated in5 kgs. of toluol with an excess of lead-carbonate under vigorousstirring and at a temperature of approximately 100 C. The thus formedleadsuliide is filtered off and the solution is applicable for theimpregnation after dilution to the desired degree.

Artificial silk-satin, treated for 10 minutes with a 1% solution dilutedwith benzine and then dried for 2 hours at temperatures gradually risingto C., is of a soft handle. At the-same time this impregnationeliminates the water absorptive power. Thoseeifects could not be reducedeven by washing several times in a'0.5%-solution of soap-flakes. Thewater repellant property remained after a washing with benzine.

Example 1 kg. of hexadecoxy-pphenyl-Inustard oil is 120-130 withvigorous stirring of '7 kgs. of

soluble in organic solvents like mass(mono-hexa-decoxy-p-phenyl-carbodiimide orhexa-decoxy-pphenyl-cyanamide). The product is suitable for impregnatingwool,

cotton, mixed tissues and the like to render them water repellent. Anartificial silk-satin impregnated for minutes with a 0.5-l%-solution inbenzol and subsequently treated (as per Example 2) has a very remarkablewater-repelling power which is fast to washing. In a similar way materias of wool or mixed fibers can be impregnated to become water-repellent.

amide (boiling point 78 0.), is produced by converting octadecyl-aminewith an equi-molecular amount of chloro-acetyl-chloride in the presenceof pyridine, and 0.2 kg. of the mo'no-sodium-salt of cyanamide, .suchmixture is heated up to dibutyl ether and a small amount ofcopper-bronze powder. After removal of sodium-chloride one filters oil?from the precipitated salt and the, solvent distilled off. The thusobtained residue is a waxlike mass solid at mom-temperature and iseasily such as benzine, benzol etc. This mass dissolved in benzol issuitable for treatment of fibers in a manner similar to that of thepreceding examples for providing water-repellence.

We claim:

l. The method for improving textile material characterized byimpregnating the textile material by a carbodiimide compound containingat least one higher molecular alkyl radical having at least 10 carbonatoms, and heating the. impregnated material at temperatures above 100C. to produce a reaction by the said compound to producewater-repellency in the fibre.

2. The method for improving textile, material characterized byimpregnating the textile material by a carbodiimide compound containingat least one higher molecular hydrocarbon radical of the groupconsisting of alkyl, arallml, alkylaryl radicals having at least 10carbon atoms in the 'alkyl portion thereof, and heating the impregnatedmaterial at a temperature between 105-l20 C. to produce a reactionproduce water-repellency in the fibre.

3. The method for improving textile material characterized byimpregnating the textile material by a carbodiimide compound containingat 'therein, and heating the by the said compound to g least one highermolecular alkyl radical having at least 10 carbon atoms, having at leastone hetercatom in the a iphatic chain and heating the impregnatedmaterial to, produce a reaction by the said compound to producewater-repellency in the fibre.

4. The method for improving textile material characterized byimpregnating the textile material by a carbodiimide compound containingat least one higher molecular aliphatic radical having no less than 10carbon atoms and heating the impregnated material to produce a reactionby the said compound to produce water-repellency in the fibre.

- 5. The method for improving textile material characterized byimpregnating the textilematerial by a diarylcarbodiimide having at leastonealkyl radical in the compound containing no less than 10 carbon atomsand heating the impregnated material to produce a reaction bythe saidcompound to produce water-repellency in the fibre.

6. The method for improving textile material characterized byimpregnating the textile material by a carbodiimide compound containingan alkyl-aryl radical having an oxygen atom in the hydrocarbon chain andat least 10 carbon atoms impregnated material to produce a reaction bythe said compound to produce water-repellency in the fibre.

7. The method for improving textile material characterized byimpregnating the textile material by a carbodiimide compound containingan aliphatic radical having an -+NHCO group carbon atoms.

. WINFRID HENTRICH. RICHARD HUETER. HEINZ-JOACEIM ENGELBRECHT.

CERTIFICATE OF CORRECTI'CYN, V 4 Patent No. 2,365,750. I November 25,19L 1.

WINFRID HENTRICH, ET AL. V Y

' It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as fiollows: Page 1,first column, line 51, for the wordsfiepplied material read.-materialapplied-; line 50,"for diaryi -varbodi read diaryi-carhodipage 2, firstcolumn, line 17,4101- 1eafsu1fide" read "legi -sulfide"; page 5, firstcolumn, line 20; after "stirring" insert in the. preserijce j line "25,.after "solvent" insert -is--' and theft the aid LettersP'Zi-te nt'shouldbe read with this correction therein that the same meg: confornrtothe record of the case in the Patent Office. 1 1 Signed and sealed this15th day of Jarr'jary, A ."-'B..l9h.2.

n 1 Henry Van Arsdalle, O (Seal) e Acting Commissioner of Patents

